Photoelectrochemical Conditioning of MOVPE p-InP Films for Light-Induced Hydrogen Evolution: Chemical, Electronic and Optical Properties

Homoepitaxial p-InP(100) thin films prepared by MOVPE (metallorganic vapor phase epitaxy) were transformed into an InP/oxidephosphate/Rh heterostructure by photoelectrochemical conditioning. Surface sensitive synchrotron radiation photoelectron spectroscopy indicates the formation of a mixed oxide constituted by In(PO3)(3), InPO4 and In2O3 as nominal components during photo-electrochemical activation. The operation of these films as hydrogen evolving photocathode proved a light-to-chemical energy conversion efficiency of 14.5%. Surface activation arises from a shift of the semiconductor electron affinity by 0.44 eV by formation of In-Cl interfacial dipoles with a density of about 10(12) cm(-2). Predominant local In2O3-like structures in the oxide introduce resonance states near the semiconductor conduction band edge imparting electron conductivity to the phosphate matrix. Surface reflectance investigations indicate an enhanced light-coupling in the layered architecture. (C) 2013 The Electrochemical Society. All rights reserved.